Ink composition containing a blend of a polyester, an acrylic polymer and a vinyl polymer

ABSTRACT

Disclosed is a novel blend of a water-dissipatable polyester material, an acrylic polymer and a water-dissipatable vinyl polymer. The acrylic polymer and the vinyl polymer must be compatible with the polyester. The polyester is exemplified in having an acid component of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodiosulfoisophthalic acid, and having a glycol component of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 44 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof. 
     The polymer blends are useful for preparing ink compositions having improved block resistance, water resistance, and alcohol resistance.

This is a divisional of copending application Ser. No. 07/256,344 filedon Oct. 11, 1988, now U.S. Pat. No. 4,921,899.

FIELD OF INVENTION

The present invention relates to a novel polymer blend useful inprinting inks which contains a linear, water-dissipatable polyester orpolyesteramide material in combination with an acrylic polymer and awater-dissipatable vinyl polymer.

BACKGROUND OF THE INVENTION

Inks containing a water-dissipatable polyester or polyesteramide arewell known in the art (see, for example, U.S. Pat. Nos. 4,704,309 and4,738,785). Inks containing such a polymeric material have manydesirable properties such as good adhesion to a variety of substratesand a wide viscosity range. However, despite the advantages obtainedusing such a polymeric material in aqueous inks, it is known thataqueous inks with such a polymer by itself have been alleged to haveproblems, namely poor water resistance and poor block resistance on somesubstrates (e.g., see Japanese Kokai 57-10663).

In addition, alcohol resistance is a desirable property of inks for someapplications. In particular, alcohol/menthol resistance is desirable (aswell as water and block resistance) in inks used in the tobacco industryfor printing onto cigarette packaging. It would be highly desirable tohave a material that imparts good water resistance, block resistance,and alcohol resistance while maintaining the other advantages associatedwith the use of the water-dissipatable polyester or polyesteramide.

SUMMARY OF THE INVENTION

It has now been discovered that the water-dissipatable polyestermaterial as described herein, when mixed with an acrylic polymer andwater dissipatable vinyl polymer, will provide to ink compositions goodwater resistance, good block resistance, and good alcohol resistancewithout concomitant substantial sacrifice of the advantages obtained byuse of the water-dissipatable polyester material alone. This polymerblend can be used to prepare water-based inks, ink overprints and inkprimers, which shall be referred to herein collectively as "inkcompositions." More specifically, the present invention is directed to apolymer blend comprising:

(A) About 10 to 65 weight percent, based on the weight of (A) plus (B)plus (C) of one or more water-dissipatable or dispersible polymershaving carbonyloxy linking groups (i.e., ester groups of the formula##STR1## in the linear molecular structure wherein up to 80% of thelinking groups are carbonylamido linking groups, (i.e., amide groups ofthe formula ##STR2## the polymer having an inherent viscosity of fromabout 0.1 to about 1.0 measured in a 60/40 parts by weight solution ofphenol/tetrachloroethane at 25° C. and at a concentration of 0.25 gramof polymer in 100 mL of the solvent, the polymer containingsubstantially equimolar proportions of acid equivalents (100 mole %) tohydroxy and amino equivalents (100 mole %), the polymer comprising thereaction products of reactants selected from (a), (b), (c), and (d), orthe ester forming or esteramide forming derivatives thereof, as followswherein all stated mole percentages are based on the total of all acid,hydroxyl and amino equivalents being equal to 200 mole %:

(a) at least one difunctional dicarboxylic acid;

(b) from about 4 to about 25 mole % of at least one difunctionalsulfomonomer containing at least one metallic sulfonate group ornitrogen-containing non-metallic sulfonate group attached to an aromaticor cycloaliphatic nucleus wherein the functional groups are hydroxy,caboxyl or amino;

(c) at least one difunctional reactant selected from a glycol or amixture of a glycol and diamine having two --NRH groups, the glycolcontaining two --CH₂ --OH groups of which

(1) at least 15 mole % is a poly(ethylene glycol) having the structuralformula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of from 2 to about 20, or

(2) of which from about 0.1 to less than about 15 mole % is apoly(ethylene glycol) having the structural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of between 2 and about 500, and with the proviso thatthe mole % of said poly(ethylene glycol) within said range is inverselyproportional to the quantity of n within said range; and

(d) from none to about 40 mole % of difunctional reactant selected fromhydroxycarboxylic acids having one --C(R)₂ --OH group, aminocarboxylicacids having one --NRH group, amino-alcohols having one --C(R)₂ --OHgroup and one --NRH group, or mixtures of said difunctional reactants;

wherein each R in the (c) and (d) reactants is a hydrogen atom or analkyl group of 1 to 4 carbons,

(B) an acrylic polymer in an amount of about 15 to 30 percent, based onthe total weight of Components (A) plus (B) plus (C), said acrylicpolymer being compatible with the water-dissipatable polyester at amaximum acrylic polymer concentration of about 60/40 weight percent ofthe total acrylic/polyester polymer solids, and

(C) a water-dissipatable vinyl polymer in an amount of about 20 to 60weight percent, based on the weight of (A) plus (B) plus (C), said vinylpolymer being compatible with the water-dissipatable polyester at amaximum vinyl polymer concentration of about 60/40 weight percent of thetotal vinyl/polyester polymer solids.

The present invention is also directed to an ink composition made fromthe polymer blend of this invention comprising:

(I) about 5 to 40 weight percent of the polymer blend,

(II) about 0 to 45 weight percent of at least one colorant, and

(III) about 35 to 95 weight percent of water.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "water-dissipatable polyester","water-dissipatable polyester material", "polyester material", or"polyester" refers to Component (A) described hereinabove, "acrylicpolymer" refers to Component (B) described hereinabove, "vinyl polymer"refers to Component (C) described hereinabove, and "polymer blend"refers to a blend of Component (A), Component (B), and Component (C).

Whenever the term "water-dissipatable" or "water-dispersible" is used inthis description, it will be understood to refer to the activity of awater or aqueous solution on the applicable polymer. The term isspecifically intended to cover those situations wherein the solutiondissolves and/or disperses the polymer material therein and/ortherethrough.

By the phrase "an amount effective to increase the block resistance orwater resistance properties of . . . " is meant that amount of acrylicpolymer that, when added to the water-dissipatable polyester, willincrease the block resistance and/or water resistance of an inkcomposition as compared to a comparable ink composition without saidacrylic polymer.

By the phase "an amount effective to increase the alcohol resistanceproperties of . . . " is meant that amount of vinyl polymer that, whenadded to a blend of water dissipatable polyester and acrylic polymer,will increase the alcohol resistance of an ink composition as comparedto a comparable ink composition without said vinyl polymer. It ispreferred that the water resistance of ink compositions made from thepolymer blend of the present invention is at least good; more preferredis excellent. It is also preferred that the alcohol resistance is atleast good. It is also preferred, concerning block resistance, that theink compositions made from the polymer blend of the present invention donot block above about 100° F. (37.78° C.); more preferably do not blockabove about 120° to 220° F. (48.89° to 104.44° C.), for 5 seconds on aSentinel Heat Sealer at 40 psi (275.79 kilopascal). Water resistance canbe determined by the procedure described in Example 5. Block resistancecan be determined by the procedure described in Example 7. Alcoholresistance can be determined by the procedure described in Example 5.

By the term "compatible" is meant that a 60/40 weight blend ofacrylic/polyester polymer or vinyl/polyester polymer (or a blend with,appropriately, less acrylic polymer or less vinyl polymer) will not gelor have a significant increase in viscosity after being held at 120° F.(48.89° C.) for 24 hours or at room temperature for 14 days. By the term"gel" or "gelling" is meant that the blend is not pourable at roomtemperature. A significant viscosity increase after 24 hours at 120° F.(48.89° C.) is typically at least two or three times the viscosity atzero time. The acrylic polymers which are compatible at the higheracrylic concentrations of the polymer blends are preferred. For example,acrylic polymers that are compatible in acrylic concentrations up to a60/40 weight blend of acrylic/polyester are preferred over acrylicpolymers that are compatible only up to a 50/50 weight blend ofacrylic/polyester. Preferred acrylic polymers are compataible at acrylicconcentrations of at least 30/70 (weight blend of acrylic/polyester)(i.e., at least 30 weight percent acrylic polymer) and more preferredacrylic polymers are compatible at acrylic concentrations of at least40/60 (i.e., at least 40 weight percent acrylic polymer). Likewise, thevinyl polymers which are compatible at the higher vinyl concentrationsof the polymer blends are preferred. For example, vinyl polymers thatare compatible in vinyl concentrations of up to a 60/40 weight blend ofvinyl/polyester are preferred over vinyl polymers that are compatibleonly up to a 50/50 weight blend of vinyl/polyester. Preferred vinylpolymers are compatible at vinyl concentrations of at least 30/70(weight blend of vinyl/polyester) (i.e., at least 30 weight percentvinyl polymer) and more preferred vinyl polymers are compatible at vinylconcentrations of at least 50/50 (i.e. at least 50 weight percent vinylpolymer).

In the polymer blend of the present invention it is preferred thatComponent (B) is present in an amount effective to increase the blockresistance or water resistance properties of Component (A) whenformulated into an ink composition; also, preferably, Component (B) ispresent in an amount of about 20 percent. It is preferred that Component(C) is present in an amount effective to increase the alcohol resistanceproperties of Component (A) and Component (B) when formulated into anink composition; also, preferably, Component (C) is present in an amountof about 30 percent. Component (A) is present in an amount of about 10percent to 65 percent, more preferably about 50 percent. Thesepercentages are based on the total weight of Components (A), (B), and(C).

In the ink compositions of the present invention it is preferred thatComponent (I) is present in an amount of about 5 to 40 weight percent,that Component (II) is present in an amount of about 0 to 35 weightpercent, and that Component III is present in an amount of about 35 to95 weight percent. If the ink composition is a finished ink, it ispreferred that at least about 0.5 weight percent of colorant is present.More typically, in inks, at least about 5 weight percent of colorant ispresent. If the ink composition contains an organic pigment, typicallysuch an organic pigment is present in an amount of about 17.5 weightpercent or less of the total composition. If the ink compositioncontains an inorganic pigment, typically such inorganic pigment ispresent in an amount of about 50 weight percent or less of the totalcomposition.

The ink compositions can optionally contain up to about 10 weightpercent, preferably up to about 3 weight percent of one or moreadditives. Such additives include waxes such as Jonwax 26, Jonwax 120(available from S. C. Johnson and Sons, Inc., Racine, Wis. 53403;U.S.A.), or Vanwax 35 (available from Vantage, Garfield, N.J. 07026);surfactants such as Surfynol 104 and Surfonyl 440 (available from AirProducts and Chemicals, Allentown, Pa. 18105); modifiers (for example,defoamers) such as WBT-409, Resolv (available from Vantage), Carbowet990 (available from Vantage), OT-70 aerosol (available from McIntyre,Chicago, Ill. 60632), Foamaster 111 (available from Henkel Corporation,Morristown, N.J. 07960); alcohols such as n-propyl alcohol, isopropylalcohol, propylene glycol, ethylene glycol monobutyl ether, or ethyleneglycol; biocides; pH stabilizers; dispersants; thickeners such asAcrysol RM-825 (available from Rohm & Haas, Philadelphia, Pa. 19105);and the like.

Typically, it is desirable to add a small amount of one or more pHstabilizers to the ink compositions to keep the pH within a desiredrange. For example, it is common to add about 0.1 weight percent sodiumacetate to an ink or aqueous solution/dispersion of polymer blend.

Preferred amounts of certain additives in ink compositions of thepresent invention are set forth in the following table.

    ______________________________________                                        Component      Weight Percent                                                 ______________________________________                                        Wax.sup.(a)    0.0-3.0                                                        Surfactant.sup.(b)                                                                           0.0-3.0                                                        Modifier.sup.(c)                                                                             0.0-2.0                                                        Alcohol.sup.(d)                                                                              0.0-8.0                                                        ______________________________________                                         .sup.(a) e.g., Jonwax 26, 120, Vanwax 35                                      .sup.(b) e.g., Surfyno1 104, 440                                              .sup.(c) e.g., WBT409, Resolv, Carbowet 990, Aerosol OT70 Foamaster 111       .sup.(d) e.g., nPropyl Alcohol or Isopropyl Alcohol; Propylene Glycol,        Ethylene Glycol Monobutyl Ether                                          

In the water-dissipatable polyester useful in the present invention, themetallic portion of the metallic sulfonate group is preferably amonovalent metal such as Na⁺, K⁺, or Li⁺. The nonmetallic portion of thenonmetallic sulfonate group is a nitrogen-based cation derived fromnitrogen-containing bases which may be aliphatic, cycloaliphatic oraromatic basic compounds that have ionization constants in water at 25°C. of 10⁻³ to 10⁻¹⁰, preferably 10⁻⁵ to 10⁻⁸. Especially preferrednitrogen containing bases are ammonia, dimethylethanolamine,diethanolamine, triethanolamine, pyridine, morpholine, and piperidine.Such nitrogen-containing bases and cations derived therefrom aredescribed in U.S. Pat. No. 4,304,901, incorporated herein by reference.

In the water-dissipatable polyester it is preferred that very minor,e.g., less than about 10 mol percent based on all reactants, of reactant(d) is employed, that at least about 70 mol percent of reactant (c) isglycol, and that at least about 70 mol percent of all the hydroxyequivalents is present in the glycol. It is also preferred that asubstantial portion of reactant (c) is a cycloaliphaticdimethanol, e.g.,up to 50 mole percent of a cycloaliphaticdimethanol such as1,4-cyclohexanedimethanol.

In preferred other embodiments of the invention:

the water-dissipatable polyester material comprises an acid component(moiety) of from about 75 to about 84 mole percent isophthalic acid andconversely from about 25 to 16 mole percent 5-sodiosulfoisophthalicacid, and a glycol component (moiety) of from about 45 to about 60 mole% diethylene glycol and conversely from about 55 to 40 mole percent1,4-cyclohexanedimethanol or ethylene glycol (the term "moiety" as usedherein designates the residual portion of the reactant acid or glycolwhich actually enters into or onto the polymer chain during thecondensation or polycondensation reaction);

the inherent viscosity of the water-dissipatable polyester material isfrom about 0.28 to about 0.35, said acid component (moiety) comprisesfrom about 80 to about 83 mole percent isophthalic acid and converselyfrom about 20 to about 17 mole percent 5-sodiosulfoisophthalic acid, andthe glycol component (moiety) comprises from about 52 to about 56 molepercent diethylene glycol and conversely from about 48 to about 44 molepercent 1,4-cyclohexanedimethanol;

the ink composition is printed onto a substrate selected from metalfoil, newsprint, bleached and unbleached Kraft paper, clay coated paper,glass, calendered paper, stainless paper, paper board, and films orother substrates of polyester, polycarbonate, cellulose ester,regenerated cellulose, poly(vinylidene chloride), polyamidepolypropylene, polyethylene or polystyrene; and

after the ink composition is printed, a substantial portion of theinitial metal cations of the water solubilizing sulfonate groups of thewater-dissipatable polyester material has been replaced with aninsolubilizing polyvalent metal cation, such as Al⁺³, Ca⁺⁺, or the likeas disclosed and in the manner described in U.S. Pat. Nos. 4,145,469,and 4,704,309, the disclosures of which are incorporated herein byreference in their entirety. As stated therein, generally, based on theweight of the polymeric material, 0.05 percent to about 2.0 percent byweight solids of the polyvalent metal cation are required for effectiveinsolubilization.

The inherent viscosities (I.V.) of the particular water-dissipatablepolyester materials useful herein range from about 0.1 to about 1.0determined according to ASTM D2857-70 procedure, in a Wagner Viscometerof Lab Glass, Inc., of Vineland, N.J., having a 1/2 mL capillary bulb,using a polymer concentration about 0.25% by weight in 60/40 by weightof phenol/tetrachloroethane. The procedure is carried out by heating thepolymer/solvent system at 120° C. for 15 minutes, cooling the solutionto 25° C. and measuring the time of flow at 25° C. The I.V. iscalculated from the equation ##EQU1## where: (n)=inherent viscosity at25° C. at a polymer concentration of 0.25 g/10 mL of solvent;

ln=natural logarithm;

t₂ =sample flow time;

t_(o) =solvent-blank flow time; and

C=concentration of polymer in grams per 100 mL of solvent=0.25.

The units of the inherent viscosity throughout this application are indeciliters/gram. It is noted that higher concentrations of polymer,e.g., 0.50 g of polymer/100 mL solvent may be employed for more preciseI.V. determinations.

As appreciated in the art, the exact components and properties ofcomponents desired for any given ink application can vary, and,therefore, routine experimentation may be required to determine theoptional components and proportions of components for a givenapplication and desired properties.

The acrylic polymers useful in the present invention are commerciallyavailable and/or can be made using conventional techniques known in theart. The molecular weight of the acrylic polymer is at least about10,000 and preferred is at least about 200,000.

It is preferred that the acrylic polymer useful in the present inventionhas an acid number of about 200 or less; more preferred is less thanabout 55 and most preferred is less than about 50. It is also preferredthat the glass transition temperature (Tg) of the acrylic polymer isgreater than about 0° C.

The acrylic polymer of the present invention preferably comprisesrepeating units of the formula: ##STR3## wherein R' is H, a straight,branched, or cyclic alkyl group of 1 to 20 carbon, preferably 1 to 10carbon atoms, optionally substituted with up to 2 substituents such asC₁ -C₆ alkoxy or halogen such as chloro- or bromo; and R" is H ormethyl. More preferably R' is H, methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, hexyl, heptyl, 2-ethylhexyl,2-ethylbutyl, dodecyl, hexadecyl, 2-ethoxyethyl, or cyclohexyl.

The acrylic polymer can optionally be styrenated and therefore furthercomprise repeating units of the formula: ##STR4##

The acrylic polymer can also be a copolymer containing repeating unitsderived from an acrylonitrile monomer.

The acrylic polymer can be blended with the polyester material and/orvinyl polymer in pure form or either or both or all three polymers canbe in a mixture with water or an aqueous solution. The mixture of theacrylic polymer and water or aqueous solution can be in the form of awater-borne alkali soluble resin, a colloidal dispersion, or emulsion.Preferred for use is an emulsion or dispersion of an acrylic polymerhaving a pH of about 7.5-9.0 and a Brookfield viscosity of about200-1,000 centipoise (cp) at 25° C. Also preferred is an emulsioncontaining about 25-55 weight percent of acrylic polymer (more preferredabout 45-50 weight percent) with the remainder of the emulsion beingwater or aqueous solution. If an aqueous solution is used to make theaqueous emulsion or dispersion of acrylic polymer, such emulsion ordispersions will contain one or more additives typically used in the artin amounts of to about 5 weight percent of the emulsion or dispersion,preferably about 1 to about 3 weight percent. Such additives can beemulsion stabilizers, surfactants, dispersants, antimicrobials orbiocides, pH stabilizers, and the like. The additives described hereinas suitable for use in the ink compositions are also suitable for usewith the mixture of acrylic polymer and aqueous solution. The followingTable 1 lists certain acrylic polymer emulsions (except for Joncryl 67which is a solid or flake) commercially available and certain propertiesthereof. The acrylics having the tradename "Joncryl" are available fromS. C. Johnson and Sons, Inc., Racine, Wis. 43403, U.S.A. and theacrylics having the tradename Vancryl are available from Vantage.

                                      TABLE 1                                     __________________________________________________________________________                         Molecular   Glass  Min.      Viscosity of                      Commercial                                                                           % Polymer of                                                                          Weight                                                                              Acid No.                                                                            Trans. Temp.                                                                         Filming                                                                            pH of                                                                              Emulsion                    Type  Name   Nonvolatile                                                                           of Polymer                                                                          of Polymer                                                                          of Polymer                                                                           Temp.                                                                              Emulsion                                                                           25° C.,              __________________________________________________________________________                                                      CPS                         Acrylic                                                                             Joncryl 77                                                                           46      >200,000                                                                            55    21     20   8.3  500                         Emulsion                                                                      Styrenated                                                                          Joncryl 87                                                                           48.5    >200,000                                                                            40    100    >80  8.3  500                         Acrylic                                                                       Emulsion                                                                      Styrenated                                                                          Joncryl 134                                                                          44.0    >200,000                                                                            35    95     780  8.3  200                         Acrylic                                                                       Emulsion                                                                      Styrenated                                                                          Joncryl 1535                                                                         37.0    >200,000                                                                            30    20     15   7.5  200                         Acrylic                                                                       Emulsion                                                                      Acrylic                                                                             Joncryl 537                                                                          46.0    >200,000                                                                            40    44     42   9.0  150                         Emulsion                                                                      Styrenated                                                                          Joncryl 619                                                                          49.0    >200,000                                                                            36    97     35   8.2  950                         Acrylic                                                                       Emulsion                                                                      Styrenated                                                                          Vancryl 930                                                                          46.0    --    --    --     --   8.7  200                         Acrylic                                                                       Emulsion                                                                      Acrylic                                                                             Joncryl 74                                                                           48.5    >200,000                                                                            50    -16    <5   8.3  500                         Emulsion                                                                      Solid Joncryl 67                                                                           98        10,000                                                                            190   70     --   --   --                          __________________________________________________________________________

The water-dissipatable vinyl polymers useful in the present inventionare commercially available and/or can be made using conventionaltechniques known in the art. The vinyl polymer useful in the presentinvention comprises repeating units of the formula: ##STR5## wherein Xis halo. The term "halo" as used herein means Cl, Br, or F. It is mostpreferred that X is Cl.

The average molecular weight of the vinyl polymer is preferably about4,000-50,000. The preferred glass transition temperature (Tg) of thevinyl polymer is about 0°-100° C. In addition, the vinyl polymerpreferably contains about 20-50 weight percent halide.

The vinyl polymer can optionally contain repeating units of ethylene,vinyl acetate, acrylic acid, acrylamide, esters of acrylic acid,substituted acrylamide, and the like. Accordingly, preferred vinylpolymers also comprise repeating units such as of the formulas: ##STR6##wherein Z is NH₂ or OH; R' is as described hereinabove; and Y is apolycarboxylic acid-containing C₁ to C₂₀ alkyl chain. Also, the vinylpolymer can optionally be substituted with hydroxyl groups on thepolymer backbone.

If a mixture of the vinyl polymer is used with water or an aqueoussolution, it can be in the form of suspension, dispersion, or emulsion.Preferred for use is an emulsion or dispersion of a vinyl polymer havinga pH of about 5-9, a Brookfield viscosity of about 25-4000 cp at 25° C.(more preferred is about 25-2000 cp). Also preferred is a dispersion oremulsion of vinyl polymer containing about 25-60 weight percent of vinylpolymer (more preferred is about 45-55 weight percent) with theremainder of the dispersion being water or an aqueous solution. If anaqueous solution is used to make the aqueous dispersion or emulsion ofvinyl polymer, such dispersion or emulsion will contain one or moreadditives typically used in the art in amounts up to about 5 weightpercent of the emulsion or dispersion, preferably about 1 to about 3weight percent. Such additives can be the same as used in the dispersionor emulsion of acrylic polymer. The following Table 2 lists certainvinyl polymer dispersions or emulsions commercially available andcertain properties thereof. The vinyl polymers having the trade name"Airflex" are available from Air Products and Chemicals, Inc.,Allentown, Pa. 18105, U.S.A.; and the vinyl polymers having the tradename "UCAR" are available from Union Carbide Corporation, Danbury, Conn.06817-0001, U.S.A.

                  TABLE 2                                                         ______________________________________                                                            %                   Viscosity                                        Com-     Non    Glass        of                                               mercial  Vol-   Trans.                                                                              pH of  Emulsion                              Type       Name     atiles Temp. Emulsion                                                                             25° CPS                        ______________________________________                                        Ethylene-Vinyl                                                                           Airflex  50      0    7-9    25-150                                Chloride   4500                                                               Emulsion                                                                      Ethylene-Vinyl                                                                           Airflex  50     14    7-9    25-150                                Chloride   4514                                                               Emulsion                                                                      Ethylene-Vinyl                                                                           Airflex  50     30    30     25-150                                Chloride   4530                                                               Emulsion                                                                      Ethylene-Vinyl                                                                           Airflex  48     22    5-6    150-400                               Chloride   7522 Dev                                                           Emulsion                                                                      Waterborne Vinyl                                                                         UCAR     31     60    6.7-7.7                                                                              2000                                  Dispersion AW-100                                                             ______________________________________                                    

Of course, it is contemplated that two or more polyester materials, twoor more vinyl polymers, and/or two or more acrylic polymers can be usedin the present invention. The water-dissipatable polyester can be madeby known techniques, for example, by those disclosed in U.S. Pat. Nos.3,734,874; 3,779,993; and 4,233,196; the disclosures of which areincorporated herein by reference in their entirety.

The aqueous solution or dispersion of water-dissipatable polyester to beblended with the acrylic polymer dispersion and/or vinyl polymerdispersion preferably comprises about 26 to 38 weight percent ofpolyester material with the remainder being water or an aqueoussolution. The aqueous solution can be the same or be similar to theaqueous solution used to make the aqueous dispersion or emulsion ofacrylic polymer, with the amount of additives being present in an amountof up to about 5 weight percent, preferably about 1 to about 3 weightpercent.

The ink compositions of this invention can be for any of the typical inkapplications such as flexographic, gravure, letterpress, ink-jet, orscreen-process printing applications. The ink compositions of thepresent invention have excellent adhesion to a wide variety ofsubstrates including plastic films such as polyester, polyethylene orpolypropylene; aluminum foil; glass; and paper.

The ink compositions of the present invention should have a pH of about8.2 or lower; preferred is a pH of about 7 to 8. If the pH is higherthan about 8.2, there is a danger of the polymer(s) hydrolyzing whichresults in gelling of the system.

The polyester material can be dispersed in water or aqueous solutionusing the techniques described herein or known in the art and thenblended with an aqueous dispersion or emulsion of acrylic polymer and/orvinyl polymer prepared by similar techniques, or blended with an aqueousemulsion or dispersion of acrylic polymer and/or vinyl polymer in a formcommercially available. The following procedure can be used fordispersing the polyester in water: The water should be preheated toabout 180° F. (82.22° C.) to about 200° F. (93.33° C.) and the polyesterin pellet form is added rapidly to the vortex under high shear stirring.A Cowless Dissolver, Waring Blender, or similar equipment may be used.Once the water is heated to the desired temperature, additional heatinput is not required. Depending upon the volume prepared, dispersion ofthe pellets should be complete within 15 to 30 minutes stirring.Continued agitation with cooling may be desirable to prevent thickeningat the surface due to water evaporation. Viscosities of the dispersionsremain low up to polyester levels of 25 percent to 30 percent andviscosities increase sharply above these levels. Viscosities of thedispersions will be influenced by the degree of polymer dispersionobtained which is affected by the dispersing temperature, shear, andtime. The polyester blend content typically may range from about 15percent to about 50 percent by weight of the aqueous dispersion with thepreferred for most applications being from about 26 percent to about 38percent.

The inks, overprints, and primers of this invention can be prepared, forexample, as disclosed in U.S. Pat. No. 4,148,779, which is incorporatedherein by reference in its entirety. For example, the printing ink,overprint, or primer may be prepared as follows: The colorant is addedto the polymer blend dispersion and, at a properly adjusted viscosity,dispersed thereinto with ball mill, sand mill, high-shear fluid flowmill, Cowles Dissolver, Katy Mill or the like. The colorants also may bedispersed directly in the polymer by milling on a heated two-roll millat about 220° to 360° F. (104.44° to 182.22° C.) and using processingaids as desired, such as solvents or plasticizers. The viscosity andprinting characeristics of the ink composition may be modified furtherby addition of water, solvents, plasticizers, sequestered wax,surfactants and the like to suit the particular printing needs. Theamounts and nature of these optional additives have been previouslydescribed herein.

The present invention is not limited to any type of dye, pigment,filler, or the like, all of which are hereinafter included in the term"colorant," and can accommodate any colorant which can be dispersed,milled, mixed, blended or dissolved in any manner in either the polymerblend, water or aqueous polymer system.

Exemplary useful C.I. pigments for use in the present invention aregiven in the following table:

    ______________________________________                                        Pigments                                                                      Generic Name      C.A. Index/Chemical Name                                    ______________________________________                                        C.I. Pigment Yellow 17                                                                          Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-bipehnyl]                                                       4,4'-diyl)bis(azo)bis                                                         [N-(2-methoxypehnyl)-3-                                                       oxo-                                                        C.I. Pigment Blue 27                                                                            Ferrate (4-1), hexakis                                                        (cyano-C)-ammonium iron                                                       (3+)(1:1:1)                                                 C.I. Pigment Red 49:2                                                                           1-Naphthalenesulfonic                                                         acid, 2-[(2-hydroxy-1-                                                        naphthalenyl)azo]-,                                                           calcium salt (2:1)                                          C.I. Pigment Red 81:1                                                                           Benzoic acid, 2,-[6-ethyl-                                                    amino)-3-(ethylimino)-2,7-                                                    dimethyl-3H-xanthen-9-yl]-,                                                   ethyl ester, w/molybdenum                                                     tungsten hydroxide oxide                                                      phosphate                                                   C.I. Pigment Red 81:3                                                                           Benzoic acid, 2-[6-ethyl-                                                     amino)-3-ethylimino)-2,7-                                                     dimethyl-3H-xanthen-9-yl]-,                                                   ethyl ester,                                                                  molybdatesilicate                                           C.I. Pigment Red 81:x                                                                           Benzoic acid, 2-[6-(ethyl-                                                    amino)-3-(ethylimino)-2,7-                                                    dimethyl-3H-xanthen-9-yl]-,                                                   ethyl ester,                                                                  molybdatephosphate                                          C.I. Pigment Yellow 83                                                                          Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]-                                                      4,4'-diyl)bis(azo)bis[N-                                                      (4-chloro-2,5-dimethoxy-                                                      phenyl)-3-oxo-                                              C.I. Pigment Red 57:1                                                                           2-Naphthalenecarboxylic                                                       acid, 3-hydroxy-4-[(4-                                                        methyl-2-sulfophenyl)azo]-,                                                   calcium salt (1:1)                                          C.I. Pigment Red 49:1                                                                           1-Naphthalenesulfonic                                                         acid, 2-[(2-hydroxy-1-                                                        naphthalenyl)azo]-,                                                           barium salt (2:1)                                           C.I. Pigment Violet 23                                                                          Diindolo[3,3',2'm]                                                            triphenodioxazine, 8,18-                                                      dichloro-5,15-diethyl-                                                        5,15-dihydro-                                               C.I. Pigment Green 7                                                                            C.I. Pigment Green 7                                        C.I. Pigment Blue 61                                                                            Benzenesulfonic acid,                                                         [[4-[[4-phenylamino)-                                                         phenyl]-[4-(phenylimino)-                                                     2,5-cyclohexadien-1-                                                          ylidene]methyl]-phenyl]                                                       amino]-                                                     C.I. Pigment Red 48:1                                                                           2-Naphthalenecarboxylic                                                       acid, 4-[(5-chloro-4-                                                         methyl-2-sulfophenyl)azo]-                                                    3-hydroxy-, barium salt                                                       (1:1)                                                       C.I. Pigment Red 52:1                                                                           2-Naphthalenecarboxylic                                                       acid, 4-[(4-chloro-5-                                                         methyl-2-sulfophenyl)azo]-                                                    3-hydroxy-, calcium salt                                                      (1:1)                                                       C.I. Pigment Violet 1                                                                           Ethanaminium, N-[9-(2-                                                        carboxyphenyl)-6-(diethyl-                                                    amino)-3H-xanthen-3-                                                          ylidene]-N-ethyl-, molyb-                                                     datetungstatephosphate                                      C.I. Pigment White 6                                                                            Titanium oxide (TiO.sub.2)                                  C.I. Pigment Blue 15                                                                            Copper, [29H, 31H-                                                            phthalocyaninato (2-)-                                                        N.sup.29, N.sup.30, N.sup.31,                                                 N.sup.32 ]-, (Sp-4-1)-                                      C.I. Pigment Yellow 12                                                                          Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]-                                                      4,4'-diyl)bis(azo)]bis[3-                                                     oxo-N-phenyl-                                               C.I. Pigment Blue 56                                                                            Benzenesulfonic acid, 2-                                                      methyl-4-[[4-[[4-[(3-                                                         methylphenyl)amino]                                                           phenyl]-[4-[(3-methyl-                                                        phenyl)-imino]-2-5-                                                           cyclohexadien-1-                                                              ylidene]methyl]-phenyl]                                                       amino]-                                                     C.I. Pigment Orange 5                                                                           2-Naphthalenol, 1-[(2,4-                                                      dinitrophenyl)azo]-                                         C.I. Pigment Black 7                                                                            Carbon black                                                C.I. Pigment Yellow 14                                                                          Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]-                                                      4,4'-diyl)bis(azo)]bis-                                                       [N-(2-methylphenyl0-3-oxo-                                  C.I. Pigment Red 48:2                                                                           2-Naphthalenecarboxylic                                                       acid, 4-[(5-chloro-4-                                                         methyl-2-sulfophenyl)-                                                        azo]-3-hydroxy-, calcium                                                      salt (1:1)                                                  C.I. Pigment Blue 15:3                                                                          Copper, [29H, 31H-                                                            phthalocyaninato                                                              (2-)-N.sup.29, N.sup.30, N.sup.31,                                            N.sup.32 ]-, (SP-4-1)-                                      C.I. Pigment Yellow 1                                                                           Butanamide, 2-[(4-methyl                                    2-nitrophenyl)azo]-3-oxo-                                                                       N-phenyl-                                                   C.I. Pigment Yellow 3                                                                           Butanamide, 2-[(4-                                                            chloro-2-nitrophenyl)                                                         azo]-N-(2-chlorophenyl)                                     3-oxo-                                                                        C.I. Pigment Yellow 13                                                                          Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]                                     4,4'-diyl)bis(azo)]bis                                                                          [N-(2,4-dimethylphenyl)-B-                                                    oxo-                                                        C.I. Pigment Orange 16                                                                          Butanamide, 2,2'-[(3,3'-                                                      dimethoxy[1,1'-biphenyl]                                    4,4'-diyl)bis(azo)]bis                                                                          [3-oxo-N-phenyl-                                            C.I. Pigment Yellow 55                                                                          Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]                                     4,4'-diyl)bis(azo)]bis                                                                          [N-(4-methylphenyl)-3-                                                        oxo-                                                        C.I. Pigment Red 41                                                                             3H-Pyrazol-3-one,4,4'-                                                        [(3,3'-dimethoxy[1,1'-                                                        biphenyl]-4,4'-diyl)bis                                                       (azo)]bis[2,4-dihydro-5-                                                      methyl-2-phenyl-                                            C.I. Pigment Orange 34                                                                          3H-Pyrazol-3-one,4,4'-                                                        [(3,3'-dichloro[1,1'-                                                         biphenyl]-4,4'-diyl)bis                                                       (azo)]bis[2,4-dihydro-5-                                                      methyl-2-(4-methylphenyl)-                                  C.I. Pigment Blue 62                                                                            4,4'-Bis(diethylamino)                                                        benzophenone condensed                                                        with N-ethyl-1-naphthyl-                                                      amine in toluene with                                                         phosphorous oxychloride                                                       and converted to the                                                          copper ferrocyanide salt                                                      (PTMA salt in P. Blue 1)                                    C.I. Pigment Red 22                                                                             2-Naphthalenecarboxamide,                                                     3-hydroxy-4-[(2-methyl-5-                                                     nitrophenyl)azo]-N-phenyl-                                  C.I. Pigment Red 170                                                                            2-Naphthalenecarboxamide,                                                     4-[[(4-(aminocarbonyl)                                                        phenyl]azo]-N-(2-ethoxy-                                                      phenyl)-3-hydroxy-                                          C.I. Pigment Red 88                                                                             Benzo[b]thiophen-3(2H)-one,                                                   4,7-dichloro-2-(4,7-                                                          dichloro-3-oxobenzo[b]thien                                 2(3H)-ylidene)-                                                               C.I. Pigment Yellow 151                                                                         A diazotized aniline                                                          derivative coupled with                                                       an acetoacetyl derivative                                                     of 5-aminobenzimidazolone                                   C.I. Pigment Red 184                                                                            A diazotized substituted                                                      aniline coupled with a                                                        derivative of 3-hydroxy-                                                      2-naphthanilide                                             C.I. Pigment Blue 1:2                                                                           Ethanaminium, N-[4-[[4-                                                       (diethylamino)phenyl]                                                         [4-(ethylamino)-1-1                                                           naphthalenyl]methylene]-                                                      2,5-cyclohexadien-1-                                                          ylidene]-N-ethyl-,                                                            [orthosilicato(4-)]                                                           hexatriacontaoxo-                                                             dodecamolybdate(4)-(4:1)                                    C.I. Pigment Red 3                                                                              2-Naphthalenol,                                                               1-[(4-methyl-2-nitro-                                                         phenyl)azo]-                                                C.I. Pigment Blue 15:1                                                                          Copper, [29H, 32H-                                                            phthalocyaninato(2-)-                                                         N.sup.29, N.sup.30, N.sup.31,                                                 N.sup.32 ]-, (SP-4-1)-                                                        or Copper, [chloro-29H,                                                       31H-phthalocyaninato                                                          (2-1)-N.sup.29, N.sup.30, N.sup.31,                                           N.sup.32 ]-                                                 C.I. Pigment Red 23                                                                             2-Naphthalenecarboxamide,                                                     3-hydroxy-4-[(2-methoxy-                                                      5-nitrophenyl)azo]-N-                                                         (3-nitrophenyl)-                                            C.I. Pigment Red 112                                                                            2-Naphthalenecarboxamide,                                                     3-hydroxy-N-(2-methyl-                                                        phenyl)-4-[(2,4,5-tri-                                                        chlorophenyl)azo]-                                          C.I. Pigment Yellow 126                                                                         A tetrazotized derivative                                                     of 3,3-dichlorobenzidene                                                      coupled with a derivative                                                     of acetoacetanilide                                         C.I. Pigment Red 169                                                                            3-Ethylamino-p-cresol                                                         condensed with phthalic                                                       anhydride, esterified                                                         with ethanol and a                                                            mineral acid, and                                                             converted to the copper                                                       ferrocyanide complex                                                          (chloride salt is C.I.                                                        Basic Red 1, PTMA salt is                                                     P. Red 81:1).                                               C.I. Pigment Orange 13                                                                          3H-Pyrazol-3-one,                                                             4,4'-[(3,3'-dichloro                                                          [1,1'-biphenyl]-4,4'-                                                         diyl)bis(azo)]bis[2,4-                                                        dihydro-5-methyl-2-phenyl-                                  C.I. Pigment Red 10                                                                             2-Naphthalenecarboxamide,                                                     4-[(2,5-dichlorophenyl)                                                       azo]-3-hydroxy-N-(4-                                                          methylphenyl)-                                              C.I. Pigment Blue 1:X                                                                           Ethanaminium, N-[4-                                                           [[4-(diethylamino)phenyl]                                                     [4-(ethylamino)-1-naphtha-                                                    lenyl]methylene]-2,5-                                                         cyclohexadien-1-ylidene]-                                                     N-ethyl-, molybdate-                                                          phosphate                                                   C.I. Pigment Yellow 42                                                                          Iron oxide (Fe.sub.2 O.sub.3)                                                 hydrate                                                     C.I. Pigment Red 101                                                                            Iron oxide (Fe.sub.2 O.sub.3)                               C.I. Pigment Brown 6                                                                            Iron oxide (Fe.sub.2 O.sub.3),                                                some FeO and                                                                  Fe.sub.2 O.sub.3.H.sub.2 0                                  C.I. Pigment Brown 7                                                                            Iron oxide (Fe.sub.2 O.sub.3)                                                 plus varying amounts of                                                       clay                                                        C.I. Pigment Brown 7:X                                                                          Fe.sub.2 O.sub.3. × MnO.sub.2                                           with varying amounts of                                                       clay                                                        C.I. Pigment Black 11                                                                           FeO.Fe.sub.2 O.sub.3                                        C.I. Pigment Metal 1                                                                            Aluminum                                                    C.I. Pigment Metal 2                                                                            Copper, zinc                                                ______________________________________                                    

In accordance with the present invention, ink compositions prepared fromthe above polymer blends may be superior over prior aqueous inkcompositions in one or more of such properties as pigment wetting,pigment stability, temperature stability (heat and freeze-thaw),nonsettling for extended periods of time, nonpolluting with respect toodor and volatile organics, nonflocculating, long "open" time in thepress fountain, wide viscosity range inks, adhesion to a variety ofsubstrates, hardness, gloss, drying rate on substrates, film-formingproperties at low temperatures without organic co-solvents, resistanceto grease, water and scuff, compatibility with other water-based inks,wet rub resistance, ink mileage characteristics (considerable waterdilution allowable at the press), ink press stability in general,printability (clean, sharp transfer without "stringing or misting"),trapping, easy clean up, nonplugging of printing plates, flexibility,redispersibility or rewetting, crinkle resistance, solvent resistance,alkali, chemical and detergent resistance, blocking resistance,lightfastness, heat resistance, slip angle, coefficient of friction,toughness, substrate wetting, hold-out, opacity, dry-rate, and no offseton the printing press (coating e.g. on tension rollers).

The following examples are to illustrate the invention but should not beinterpreted as a limitation thereon. All percentages are by weightunless otherwise indicated.

EXAMPLE 1 Polyester Preparation

A mixture of 79.5 g (0.41 mole) of dimethyl isophthalate, 26.6 g (0.09mole) of dimethyl-5-sodiosulfoisophthalate, 54.1 g (0.51 mole) ofdiethylene glycol, 37.4 g (0.26 mole) of 1,4-cyclohexanedimethanol, 1.4milliliter (mL) of a 1.0% (based on Ti) catalyst solution of titaniumtetraisopropoxide, and 0.74 gram (g) (0.009 mole) of sodium acetatebuffer is stirred and heated for two hours at 200°-220° C. Thetemperature is then raised to 275° C. and a vacuum of 0.3 millimeter(mm) is applied. Heating and stirring is continued for 1 hour underthese conditions. After cooling, the polymer obtained has an inherentviscosity (I.V.) of 0.36 and is tough and rubbery. It is dissipatable inhot water to the extent of about 29 weight percent to give a clear,slightly viscous solution. The composition of the acid moieties of thispolyester material is analyzed to be 82 mole % isophthalic acid residueand 18 mole % 5-sodiosulfoisophthalic acid residue, and of the glycolmoieties is analyzed to be 54 mole % diethylene glycol and 46 mole %1,4-cyclohexanedimethanol.

EXAMPLE 2 Polyester Dispersion Preparation

To 1,388.27 g of distilled water is added 660.0 g of polyester polymer,from Example 1 with stirring. The mixture is heated at 90° C. for twohours with stirring. The dispersion is cooled to 75° C. and 227.5 g ofn-propyl alcohol is added dropwise with stirring. The dispersion isallowed to cool to 35° C. with stirring and 13.65 g of Tekamer 38 AD(biocide) is added with stirring. The clear polyester dispersion has thefollowing composition.

    ______________________________________                                        Component            Weight, %                                                ______________________________________                                        Polyester Polymer (Example 1)                                                                      28.91                                                    n-Propyl Alcohol     10                                                       Tektamer 38AD        0.6                                                      Water                60.49                                                    ______________________________________                                    

EXAMPLE 3 Preparation of Water-Based Overprint Varnish

The overprint varnishes (OPV) are made by slowly adding Joncryl 537 andAirflex 4530 (see Table 1) to the polyester dispersion of Example 2 withstirring. The amounts of each component used and the resulting weightpercent of Joncryl and Airflex polymers (% of total polymer solids)contained in the varnish is listed in Table 2. These varnishes arestirred for five minutes and then filtered through a cheese cloth.

                  TABLE 7                                                         ______________________________________                                        Composition of Overprint Varnish                                              % Joncryl 537/                                                                Airflex 4530             % Solid                                              (40/60 Weight            Joncryl 537 and                                      Ratio)     % Polyester   Airflex 4530 Per                                     Emulsion Used                                                                            Dispersion Used                                                                             Total Polymer Solids                                 ______________________________________                                        0.00       100.0         0.00                                                 3.08       96.92         5.00                                                 6.29       93.71         10.00                                                9.63       90.37         15.00                                                13.12      86.88         20.00                                                16.76      83.24         25.00                                                20.57      79.43         30.00                                                24.55      75.45         35.00                                                28.71      71.29         40.00                                                33.78      66.22         45.78                                                ______________________________________                                    

EXAMPLE 4 Sample Preparation

The varnishes are applied on Aluminum Foil and Polypropylene with aNumber 3 and 6 Meyer rod and with a Gravure and Flexo Handproofer. Thesesamples are then allowed to dry for 24 hours at 70° F. (21.11° C.), 60%relative humidity or dried in the oven at 100° C. for 3 seconds.

EXAMPLE 5 Water Resistance and Alcohol Resistance Evaluation ofOverprints

The overprints of Example 3 are applied to aluminum foil as described inExample 4. The water resistance of the samples are determined by thewater spot test. Water Spot Test--Distilled water drops were left on thefilm surface for 1, 5, and 20 minutes, then wiped off gently with afacial tissue. The integrity of the film is visually assessed.

The water spot test is rated as follows:

1. Poor: Total film removal

2. Fair: Partial film removal

3. Good: Dull or discolor film, but no removal

4. Excellent: The film is substantially unchanged

The alcohol resistance of the samples is determined by thealcohol/menthol spot test.

Alcohol/Menthol Spot Test--The alcohol/menthol solution drops wereapplied to a printed substrate and left on the ink film surface for 1and 5 minutes, then wiped off gently with a facial tissue. The samerating system is used as for the water spot test. The composition of thealcohol/menthol solution used to test the alcohol resistance is asfollows:

    ______________________________________                                        Weight %         Ingredients                                                  ______________________________________                                        50.0000          L-menthol                                                    49.9905          Ingestible ethyl alcohol                                                      (190 proof)                                                   0.0094          Nicotine                                                      0.0001          Methylene Blue                                               ______________________________________                                    

The test results for the overprint varnishes of Table 2 are shown inTables 3A and 3B. At least 30% Joncryl 537/Airflex 4530 (total polymersolids) is shown to obtain good water resistance. The water resistanceand alcohol resistance can also be determined by a water soak test oralcohol soak test.

                                      TABLE 3A                                    __________________________________________________________________________    Effect of Joncryl 537/Airflex 4530 on                                         Water and Alcohol Resistance of Overprint Varnish                                                      Weight % Solid            Alcohol                    Weight %                 Joncryl 537 + Airflex 4530                                                                   Water Res. Rating                                                                        Resistance Rating          Joncryl 537 + Airflex 4530                                                                   Weight % Polyester                                                                      Polymers Per   (Spot Test on Foil                                                                       (Spot Test On Foil @       Emulsions Used Dispersion Used                                                                         Total Polymer Solids                                                                         20 Min.)   5 Min.)                    __________________________________________________________________________    0.00           100.00    0.00           1          4                          3.08           96.92     5.00           1          4                          6.29           93.71     10.00          1          4                          9.63           90.37     15.00          1          4                          13.12          86.88     20.00          1          4                          16.76          83.24     25.00          1          4                          20.57          79.43     30.00          3          4                          24.55          75.45     35.00          3          4                          28.71          71.29     40.00          3          4                          33.78          66.22     45.78          4          4                          __________________________________________________________________________

                  TABLE 3B                                                        ______________________________________                                        Effect of Airflex 4530 on Alcohol Resistance of                               Polyester/Joncryl 537 Overprint Varnish                                       Weight % Solid of                                                             Airflex 4530 per                                                                              Alcohol Resistance Rating                                     Total Polymer Solids                                                                          (5 Min.)                                                      ______________________________________                                         0*             1                                                              5              1                                                             10              1                                                             15              2                                                             20              3                                                              25*            4                                                             30              4                                                             35              4                                                             40              4                                                             45              4                                                             ______________________________________                                         *75 wt. % polyester and 25 wt. % Joncryl 537 (total polymer solids)           *25% Airflex 4530, 56% polyester, and 19% Joncryl (total polymer solids) 

EXAMPLE 6 Preparation of Printing Inks

An ink millbase is made by adding 100.0 g of blue pigment, PV Fast BlueB2G-A from Hoechst (Color Index Pigment Blue 15:3), 2.0 g of defoamerand 96.0 of water to 202.0 g of polyester dispersion (Example 2). Themixture is then shaken with 400.0 g of glass beads for 4 hours on apaint shaker and is filtered through cheese cloth. To 50.0 g of thefiltrate is added with stirring 49.5 g of a Joncryl 537/Airflex 4530(40/60 weight ratio) emulsion and 0.5 g of defoamer. Each ink contains12.5% pigment, 0.75% defoamer, and varying percents of the polyesterdispersion and Joncryl 537/Airflex 4530 emulsion as shown in Table 4,the percentages being by weight.

The printing inks are alternatively made by slowly adding 12.6 g ofJoncryl 537 and 19.4 g Airflex 4530, 5.3 g millbase containing HR yellow(C.I. Pigment Yellow 83) 25% pigment, 2.48 millbase containing naphtholred (C.I. Pigment Red 22) 29.8 pigment, and 3 g isopropyl alcohol to57.3 g of polyester dispersion. The ink is stirred for 5 minutes andthen filtered through a cheese cloth.

                  TABLE 4                                                         ______________________________________                                        Printing Ink Compositions                                                                             % Solid                                                           % Joncryl 537/                                                                            Joncryl 537/                                          % Polyester Airflex 4530                                                                              Airflex 4530 Per                                      Dispersion  Emulsion    Total Polymer Solids                                  ______________________________________                                        74.75       0.00        0.00                                                  72.45       2.30        5.00                                                  70.05       4.70        10.00                                                 67.55       7.20        15.00                                                 64.94       9.81        20.00                                                 62.22       12.53       25.00                                                 59.38       15.37       30.00                                                 56.40       18.35       35.00                                                 53.29       21.46       40.00                                                 49.50       25.25       45.78                                                 ______________________________________                                    

The samples and water resistance of these inks are prepared anddetermined by the same methods as used for the overprint varnishes. Theresults of the water resistance test and alcohol resistance test are inTable 5.

                  TABLE 5                                                         ______________________________________                                        Water Resistance and Alcohol Resistance                                       of Polyester Inks                                                             Weight %                                                                      Solid Joncryl 537/           Alcohol                                          Airflex 4530 Per                                                                            Water Res. Rating                                                                            Res. Rating                                      Total Polymer Solids                                                                        (Spot Test on Foil @                                                                         (Spot Test On                                    in Finished Ink                                                                             20 Minutes)    Foil @ 5 Min.)                                   ______________________________________                                        0.00          1              4                                                5.00          1              4                                                10.00         1              4                                                15.00         1              4                                                20.00         1              4                                                25.00         1              4                                                30.00         2              4                                                35.00         3              4                                                40.00         3              4                                                45.78         4              4                                                ______________________________________                                    

EXAMPLE 7 Compatibility Test

The compatibility test of the polymer blends in the ink composition ismonitored by pH readings, viscosity change and observed gelling afteraging the sample for 2 weeks in the oven at 120° F. (48.89° C.) and 4weeks at room temperature, 70° F. (21.11° C.), and also after puttingthem in the freezer at -25° F. (-31.67° C.) for 24 hours (3 cycles). Theresults of one sample are in Table 6.

                  TABLE 6                                                         ______________________________________                                        Stability of Printing Ink (With 45.78%                                        Joncryl 537 Airflex/4530 (40/60 Weight Ratio)                                 Per Total Polymer Solids)                                                     (See Table 4)                                                                                          Viscosity                                                                     (#2 Zahn Cup)                                                            pH   [Second]                                             ______________________________________                                        *Initial              7.90   19                                               *At Room Temperature 70° F. (21.11° C.)                         After 1 week          7.80   20                                               After 2 weeks         7.78   20                                               After 4 weeks         7.70   20                                               *In the Oven 120° F. (48.89° C.), 2 Weeks                                             7.74   22                                               *In the Freezer -25° F. (-31.67° C.),                                                 7.77   20                                               17 Hours, 3 Cycles                                                            ______________________________________                                    

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. An ink composition comprising(I) about 5 to 40 weightpercent of a polymer blend, comprising(A) about 10 to about 65 weightpercent, based on the weight of (A) plus (B) plus (C) of one or morelinear water-dissipatable polyesters having carbonyloxy linking groupsin the linear molecular structure wherein up to 80% of the linkinggroups are carbonylamido linking groups, the polyester having aninherent viscosity of from about 0.1 to about 1.0 measured in a 60/40parts by weight solution of phenol/tetrachloroethane at 25° C. and at aconcentration of 0.25 gram of polymer in 100 mL of the solvent, thepolyester containing substantially equimolar proportions of acidequivalents (100 mole %) to hydroxy and amino equivalents (100 mole %),the polyester comprising the reaction products of reactants selectedfrom (1), (2), (3), and (4), or the ester forming or esteramide formingderivatives thereof, as follows, wherein all stated mole percentages arebased on the total of all acid, hydroxyl and amino equivalents beingequal to 200 mole %:(1) at least one difunctional dicarboxylic acid; (2)from about 4 to about 25 mole % of at least one difunctionalsulfomonomer containing at least one metallic sulfonate group ornitrogen-containing non-metallic sulfonate group attached to an aromaticor cycloaliphatic nucleus wherein the functional groups are hydroxy,carboxyl or amino; (3) at least one difunctional reactant selected froma glycol or a mixture of a glycol and diamine having two --NRH groups,the glycol containing two --CH₂ --OH groups of which(a) at least 15 mole% is a poly(ethylene glycol) having the structural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of from 2 to about 20, or (b) of which from about 0.1to less than about 15 mole % is a poly(ethylene glycol) having thestructural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of between 2 and about 500, and with the proviso thatthe mole % of said poly(ethylene glycol) within said range is inverselyproportional to the quantity of n within said range; (4) from none toabout 40 mole % of difunctional reactant selected from hydroxycarboxylicacids having one --C(R)₂ --OH group, aminocarboxylic acids having one--NRH group, and amino-alcohols having one --C(R)₂ --OH group and one--NRH group, or mixtures of said difunctional reactants; and whereineach R in the (3) and (4) reactants is a hydrogen atom or an alkyl groupof 1 to 4 carbons; (B) an acrylic polymer in an amount of about 15 to 30percent, based on the weight of (A) plus (B) plus (C), said acrylicpolymer being compatible with the water-dissipatable polyester at anacrylic polymer concentration of 30 weight percent of the totalacrylic/polyester polymer solids, (C) a water-dissipatable vinyl polymerdifferent from the acrylic polymer (B) in an amount of about 20 to 60weight percent, based on the weight of (A) plus (B) plus (C), said vinylpolymer being compatible with the water-dissipatable polyester at avinyl polymer concentration of 30 weight percent of the totalvinyl/polyester polymer solids, and wherein said vinyl polymer comprisesrepeating units of the formula ##STR7## wherein X is halo, (II) about 0to 45 weight percent of at least one colorant, and (III) about 35 to 95weight percent of water.
 2. The ink composition of claim 1 wherein saidacrylic polymer is also compatible with the water-dissipatable polyesterat an acrylic concentration of 40/60 based on the weight of a blend ofacrylic polymer/water-dissipatable polyester, and said vinyl polymer isalso compatible with the water-dissipatable polyester at a vinylconcentration of 50/50 based on the weight of a blend of vinylpolymer/water-dissipatable polyester.
 3. The ink composition of claim 1wherein said acrylic polymer is also compatible with thewater-dissipatable polyester at an acrylic concentration of 60/40 basedon the weight of a blend of acrylic polymer/water-dissipatablepolyester, and said vinyl polymer is also compatible with thewater-dissipatable polyester at a vinyl concentration of 60/40 based onthe weight of a blend of vinyl polymer/water-dissipatable polyester. 4.The ink composition of claim 1 wherein said water-dissipatable polymerof Component (A) comprises one or more polyesters having an inherentviscosity of from about 0.28 to about 0.35, an acid moiety of from about75 to about 84 mole % isophthalic acid and conversely from about 25 toabout 16 mole % 5-sodiosulfoisophthalic acid, and a glycol moiety offrom about 45 to about 60 mole % diethylene glycol and conversely fromabout 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycolor mixtures thereof.
 5. The ink composition of claim 4 wherein said acidmoiety comprises from about 80 to about 83 mole % isophthalic acid andconversely from about 20 to about 17 mole % 5-sodiosulfoisophthalicacid, and said glycol moiety comprises from about 52 to about 56 mole %diethylene glycol and conversely from about 48 to about 44 mole %1,4-cyclohexanedimethanol.
 6. The ink composition of claim 1 whereinsaid acrylic polymer of Component (B) comprises at least one acrylicpolymer having a molecular weight of at least about 200,000, an acidnumber of less than about 55, and a Tg of greater than 0° C; andComponent (C) comprises at least one vinyl polymer having a molecularweight of 4,000-50,000, a Tg of about 0°-100° C. and a halide content ofabout 20-50 weight percent.
 7. The ink composition of claim 1 whereinsaid acrylic polymer of Component (B) comprises repeating units of theformula: ##STR8## wherein R' is H or is a straight, branched, or cyclicalkyl group of 1 to 10 carbon atoms, substituted with 0 to 2substituents selected from the group consisting of C₁ -C₆ alkoxy andhalogen; and R" is H or methyl.
 8. The ink composition of claim 7wherein R' is H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, hexyl, heptyl, 2-ethylhexyl, 2-ethylbutyl,dodecyl, hexadecyl, 2-ethoxyethyl, or cyclohexyl; and X is Cl.
 9. Theink composition of claim 7 wherein said acrylic polymer furthercomprises repeating units of the formula: ##STR9## said vinyl polymerfurther comprises one or more repeating units of the formula ##STR10##wherein Z is NH₂ or OH; R' is as previously defined; and Y is apolycarboxylic acid-containing C₁ to C₂₀ alkyl chain.
 10. The inkcomposition of claim 1 wherein Component (I) is present in an amount ofabout 5 to 40 weight percent, Component (II) is present in an amount ofabout 0 to 35 weight percent, and Component (III) is present in anamount of about 35 to 95 weight percent.
 11. The ink composition ofclaim 1 additionally comprising up to about 10 weight percent of one ormore additives.
 12. The ink composition of claim 1 additionallycontaining up to about 3 weight percent of one or more additivesselected from the group consisting of a wax, a surfactant, a defoamer,an organic solvent, a biocide, a dispersant, and a thickener.
 13. Theink composition of claim 1 having good water resistance and having theproperty of not blocking above about 100° F. for 5 seconds on a SentinelHeat Sealer at 40 psi.
 14. The ink composition of claim 1 havingexcellent water resistance and having the property of not blocking aboveabout 120° to 220° F. for 5 seconds on a Sentinel Heat Sealer at 40 psi.15. The ink composition of claim 1 having a pH of about 7 to
 8. 16. Theink composition of claim 1 wherein the colorant is one or a mixture ofthe following color index materials: C.I. Pigment Yellow 17, C.I.Pigment Blue 27, C.I. Pigment Red 49:2, C.I. Pigment Red 81:1, C.I.Pigment Red 81:3, C.I. Pigment Red 81:x, C.I. Pigment Yellow 83, C.I.Pigment Red 57:1, C.I. Pigment Red 49:1, C.I. Pigment Violet 23, C.I.Pigment Green 7, C.I. Pigment Blue 61, C.I. Pigment Red 48:1, C.I.Pigment Red 52:1, C.I. Pigment Violet 1, C.I. Pigment White 6, C.I.Pigment Blue 15, C.I. Pigment Yellow 12, C.I. Pigment Blue 56, C.I.Pigment Orange 5, C.I. Pigment Black 7, C.I. Pigment Yellow 14, C.I.Pigment Red 48:2, C.I. Pigment Blue 15:3, C.I. Pigment Yellow 1, C.I.Pigment Yellow 3, C.I. Pigment Yellow 13, C.I. Pigment Orange 16, C.I.Pigment Yellow 55, C.I. Pigment Red 41, C.I. Pigment Orange 34, C.I.Pigment Blue 62, C.I. Pigment Red 22, C.I. Pigment Red 170, C.I. PigmentRed 88, C.I. Pigment Yellow 151, C.I. Pigment Red 184, C.I. Pigment Blue1:2, C.I. Pigment Red 3, C.I. Pigment Blue 15:1, C.I. Pigment Red 23,C.I. Pigment Red 112, C.I. Pigment Yellow 126, C.I. Pigment Red 169,C.I. Pigment Orange 13, C.I. Pigment Red 1-10, 12, C.I. Pigment Blue1:X, C.I. Pigment Yellow 42, C.I. Pigment Red 101, C.I. Pigment Brown 6,C.I. Pigment Brown 7, C.I. Pigment Brown 7:X, C.I. Pigment Black 11,C.I. Pigment Metal 1, or C.I. Pigment Metal 2.